In Pohang area, basaluminite accompanying a little amounts of hydrobasalumnite, super-genetically occurs as whitish cryptocrystalline (2-4 μm) clay-like aggregates in the vicinity of altered carbonate concretions embedded within mudstones of the Tertiary Yeonil Group. A hydrobasaluminite changed readily into a basaluminite at room temperature in air, and, in turn, into a metabasaluminite when heating to 150˚~300℃. For the basaluminite, a monoclinic unit-cellparameters (a=14.845a, b=10.006a, c=11.082a, β=122.15˚) were calculated by X-ray powder diffraction data. Its basal reflections (001 and 002) are XRD analyses strongly indicate that the aluminum sulphate mineral has a layer structure and, at least, three types of water, i.e., (1) interlayer water (9.0 wt %), (2) crystal water (8.0 wt %), and (3) structural water (19.0 wt %). may present in its lattice. Based on TG-DTG data combined with EDS and IR analyses, a new chemical formula of Al5SO4(OH)134H2O was given to the basaluminite. Field occurrence and stable isotope data (δ18O, δD, δ34S) for the basaluminite seem to reflect that it was formed by the leached meteoric solution from surrounding mudstones during or after uplifting. An interaction of the acid solution with carbonate concretion and the resultant local neutralization of the fluid rich in Al3+ and SO42- are major controls on the basaluminite formation.
Textures of claystones of the Cheonunsan Formation in the Hwasoon area have been studied using optical microscope and electron microprobe. Microscopic images were observed under the optical microscope using the transmitted polarizing light from thin sections and under the electron microprobe using the back-scattered electron beam from the polished sections. Identification of minerals were made using X-ray diffraction analysis and chemical analysis by electon microprobe. Textural analyses show that the original sedimentary claystones rich in aluminium were subjected to metamorphism by which they changed to the metamorphosed claystone consisting mainly of chloritoid, quartz, andalusite and illite. Later intensive hydrothermal kaolinization of this metamorhosed claystones resulted in the formation of high-aluminous claystones rich in kaolinite exhibiting various complicated replacement textures.
Adsorption of metal elements onto illite and halloysite was investigated at 25℃ using pollutant water collected from the gold-bearing metal mine. Incipient solution of pH 3.19 was reacted with clay minerals as a function of time: 10 minute, 30 minute, 1 hour, 12 hour, 24 hour, 1 day, 2 day, 1 week, and 2 week. Twenty-seven cations and six anions from solutions were analyzed by AAs (atomic absorption spectrometer), ICP(induced-coupled plasma), and IC (ion chromatography). Speciation and saturation index of solutions were calculated by WATEQ4F and MINTEQA2 codes, indicating that most of metal ions exist as free ions and that there is little difference in chemical species and relative abundances between initial solution and reacted solutions. The adsorption results showed that the adsorption extent of elements varies depending on mineral types and reaction time. As for illite, adsorption after 1 hour-reaction occurs in the order of As〉Pb〉Ge〉Li〉Co, Pb, Cr, Ba〉Cs for trace elements and Fe〉K〉Na〉Mn〉Al〉Ca〉Si for major elements, respectively. As for halloysite, adsorption after 1 hour-reaction occurs in the order of Cu〉Pb〉Li〉Ge〉Cr〉Zn〉As〉Ba〉Ti〉Cd〉Co for trace elements and Fe〉K〉Mn〉Ca〉Al〉Na〉Si for major elements, respectively. After 2 week-reaction, the adsorption occurs in the order of Cu〉As〉Zn〉Li〉Ge〉Co〉Ti〉Ba〉Ni〉Pb〉Cr〉Cd〉Se for trace elements and Fe〉K〉Mn〉Al, Mg〉Ca〉Na, Si for major elements, respectively. No significant adsorption as well as selectivity was found for anions. Although halloysite has a 1:1 layer structure, its capacity of adsorption is greater than that of illite with 2:1 structure, probably due to its peculiar mineralogical characteristics. According to FTIR (Fourier transform infrared spectroscopy) results, there was no shift in the OH-stretching bond for illite, but the ν1 bond at 3695 cm-1 for halloysite was found to be stronger. In the viewpoint of adsorption, illite is characterized by an inner-sphere complex, whereas halloysite by an outer-sphere complex, respectively. Initial ion activity and dissociation constant of metal elements are regarded as the main factors that control the adsorption behaviors in a natural system containing multicomponents at the acidic condition.
The transformation sequence of kaolinite to mullite is examined with new electron diffraction data obtained mainly by an energy filtering transmission electron microscope. Kaolinite is transformed finally into mullite and cristobalite through several steps of continuous reactions by heating, which result in metakaolinite, microcrystalline spinel-type phase and amorphous silica. Metakaolinite maintains a short-range order in its structure ven at 920℃. Spinel phase results from a topotactictransformation of metakaolinite apart from the breakdown of metakaolinite structure. the first strong exothermic peak on DTA curve is mainly due to the extraction of amorphous silica from metakaolinite and the gradual nucleation of mullite. Metakaolinite decomposes around 940℃ to mullite that doesn't show a clear crystallographic relationship to the parent metakaolinite structure. However, spinel phase produced previously is maintained. The initially formed spinel and mullite phases are suggested to be Al-rich, but progressively gain Si in their structures at higher temperatures. Spinel phase decomposes completely through a second weak exothermic reaction promoting the growth of mullite, and crystallization of amorphous silica to cristobalite.
FORTRAN program PHYLS was developed to model the structures of 2:1 1M and 2M1 phyllosilicates on the basis of geometrical analyses. Input to PHYLS requires the chemical composition and d(001) spacing of the mineral. The output from PHYLS consists of the coordinates of the crystallographically independent sites in the unit cell, and such structural parameters as the cell dimensions, interaxial angle, cell volume, interatomic distances, and deformation angles of the polyhedra. PHYLS can generate these structural details according to the user's choice of space group and cation configuration. User can choose one of such space groups as C2/m, C2,and C2/c and such cation configurations as random and ordered tetrachedral/octahedral cation configurations. PHYLS simulated the structures of dioctahedral and trioctahedral phyllosilicates having random tetrahedral cation configuration fairly close to the reported experimentally determined structures. In contrast, the simulated structures for ordered tetrahedral cation configurations showed greater deviation from the experimentally determined structures than those for random configurations. However, if the cations were partially ordered and the sizes of the tetrahedra became similar, the simulated PHYLS may be helpful in various investigations on the relationships between structures and physicochemical properties of the phyllosilicates.